The Synthesis of Chiral Ag₄Pd₂(SR)₈ by Nonreplaced Galvanic Reaction

Abstract

Galvanic reaction is a classic reaction and widely applied in nanoscience and nanotechnology. However, it is rarely employed in the synthesis of doped metal nanoclusters with size less than ≈2 nm and remains to be exploited in nanocluster (NC) community. Herein, it is reported the synthesis of chiral Ag4Pd2(SR)8 starting from Ag25(SR)18 NC via a galvanic reaction and the characterization of the as‐obtained NC by multiple techniques such as single crystal X‐ray crystallography and X‐ray photoelectron spectroscopy.

Atomically Precise Alloy Nanoclusters

“…[178,181] Zhu and co-workerss ynthesized [Ag 4 Ni 2 (2,4-SPhMe 2 ) 8 ] 0 in 2018. [179] In 2019, Wu et al [180] [179][180][181] Each type of NC has a geometrical structure in which eight SR are coordinated to an octahedral Ag 4 M 2 core at two points. Such as tructure is similar to that of [Au 4 M 2 (SR) 8 ] 0 (M = Pt or Pd) described in Section3 .1.…”

“…[Ag 4 Pd 2 (2,4-SPhMe 2 ) 8 ] 0 has an enantiomer similar to that of [Au 4 M 2 (PET) 8 ] 0 (M = Pt or Pd) (Figure 29 D). [180] Figure 30 As hows the optical absorption spectra of [Ag 4 M 2 (DMSA) 4 ] 0 (M = Pt, Pd, or Ni). [181] As the substitution element changed from Ni to Pd to Pt, the main peak in the absorptions pectra blue shifted.…”

Ag2Au50(PET)36 Nanocluster: Dimeric Assembly of Au25(PET)18 Enabled by Silver Atoms

“…[47] X-ray photoelectron spectroscopy (XPS) studies further confirmed the synergetic interaction of Ag and Au within Ag 2 Au 50 -(PET) 36 .Itis observed from Figure S17 that the Au 4f binding energies of Ag 2 Au 50 (PET) 36 were positively shifted compared to those of Au 25 (PET) 18 ,and the Ag 3d binding energies were negatively shifted compared to those of AgÀSR complex. [48] This definitely indicates the electron transfer between Au and Ag of Ag 2 Au 50 (PET) 36 ,which is further evidenced by HOMO and LUMO predictions ( Figure S13 18 , either bonded to as taple-Auw ith E ads = À0.26 eV and n CO = 2027 cm À1 ,o rt othree staple-Auw ith E ads = À0.21 eV and n CO = 2072 cm À1 ( Figure S18 and Table S4). ForA g 2 Au 50 -(SR) 36 ,C Oc an additionally adsorb at the Ag + sites and the CÀOv ibrational stretching frequency (n CO )f or the linear Ag + ÀCO adsorption is predicted to be 1997 cm À1 ,i nr easonable agreement with the experiment (Figure S16a and Table S4).…”

Molecular reactivity of thiolate-protected noble metal nanoclusters: synthesis, self-assembly, and applications

“…The reactions between metal cations and the parent metal NCs can be accomplished by a conventional galvanic reaction. 157 These results highlight the decisive role of metal cations in the reaction with metal NCs.…”